standard operating Proiedure and checklist of Minimal Requisite Facilities lbr utilization of hazardous waste under Rule 9 of tie Hazardous and Other Wastes (Management and Transboundary movemeDt) Rules,20l6 .
Utilization' ofSpent Aluminium Chloride generated during manufacturing of CPC Green and 2,4,6-Trimethyl Benzoyl Chloride $ 'vf-1 GDffi
April,20l8
Central pollution Contiol Board (Ministry of Envlronment, Forest & Climate Change, Government of India) Parivesh Bhawan, East Arjun Nagar, Shahdara, Dethi - 110032
& standardop€ratingProcedureandchecklistofMintmalR€quistteFacitities-utitizationofspentAt!minium.- Chloride generated during manutecturing ofCpCGr€en and 2. 4, 5-Trimethyt Benzoyt Chtoride
(i) While granting authorisation for utilization of hazardous wastes. SpCBs/pCCs shall ensure the following:
a. The waste (intended for utilization) belongs to similar source of genemtlon as specified in SoPs.
b. The utilization pfoc€ss is similar to the process ofutilization described in Sops.
c. End-use / product produced from the waste shall be same as specified in Sops.
d. Authorisation be granted only after ve fication of utilization process and minimum requisite facililies as given in SoPr.
e. Issuance of passbooks (similar to the passbooks issued for recycling of used oil, waste oil, non-ferrous scrap, etc,) for maintaining records of receipt of hazardous wastes for utilization.
(ii) After issuance of authorization, SPCB shall verify the utilization process, checklist and SOPs quarterly on basis for initial 02 years; followed by random checks in the subsequent period for al leasl once a year. In-case of lack of requisite infrastructures with the SPCB/PCC, they may engage 3'dparty institutions or laboratories having EPA,/NABVISO17025 accreditation^ecognition for monitoring and analysis ofprescribed parameters in Sops for veification purpose. (iiD SPCB shall provide half yearly updated list of units permitted under Rule 9 of HOWM Rule,2016 to CPCB and also upload the same on SPCB website, periodically. Such updated list shall be senr to CPCB half yearly by July and January respectively. (iv) Authorisation for utilisation shall not be given to the units located in the State/UT where there is no Common TSDF, unless the unrt ensures authorised captive disposal of the hazardous waste (generated during utilisation)or its complete urilisation o, ur,unga."n, ofsharing with any other authorised disposal facility. (v) In case utilization proposal is not similar with respect to source of generation or utilization process or end-use as outlined in this Sop, the same may be refeired to CpCB for clarification conducting / trial utilization studiesand developing Sops thereof. (vi) The source and work zone standards suggested in the Sops are based on the E(p)A notified and OSHA standard respectively, however, SpCB/pCC may impose more stringent standards based on the location or process specific conditions. MY'
Woste Monagementlt Division, 2lP.ge C\CB Dethj standard operating Procedure and checklist ot Minimat Requisite Facitittes- uti Etion ofspent atuminium Chlorlde tenerated during manufacturlng of CpC Green and 2,4,6-Trimethyl BenzoyiChtortd€ 43.0 Utilization of Spent Aluminum Chloridel
Type ofHW Source ofgeneration Recovery/Product Spent Aluminium Chloride- Du ng the production of As a supplementary Category Serial No.- 26.3 of CPC Grcen and 2, 4, 6- rcsource to manufacture Schedule I and CZ of Trimethyl Benzoyl liquid Aluminum Hydroxide Schedule II of Hazardous Chloride Chlo del Poly Aluminum and Other Waste Chloride for further use in (Management and ETP (as coagulant) and Transboundary Movement) paper industry (as sizing Rules,2016 material) .
43.1 Source of Waste
The Spent Aluminium Chloride is geDerated during manufacturing process of CpC Green and 2, 4, 6-Trimethyl Benzoyl Chloride. The details on the manufacturing process of the above two sources is given at Appendix A. The tpical characteristics of the waste are given below:
C-hara-cteristics ofSpent Aluminium Chloride Solution Generated from CpC Green Manufacturing Industries
S. No. Parameters Unit Result 1 Moisture ok 78.09 Aluminium Chloride as 2 Alcl3 Va 18.8 3 HCls o/. 0.13 V-salt (as Sodium 4 Chloride) % 1.38
5 Calcium Chloride Vo < 0.1 Cuppers Chloride as 6 CuClz Va 1..40 '7 TOC mg&g 16.75. Heavy Metals 8 Mercury as Hg mdkg < 0.1 9 Arsenic as As mg4Ke < 0.1 10 Cadmium as Cd mdkg 0.48 11 Irad as Pb mdkg 0.62 T2 Iron as Fe mlyKg '7.2 13 Zinc as Zn ms/kg 0.84
Wdste Manogement-ll Division, CpCB Delhi 3lPage 4 standard operating Procedure and ch€ck st of MinlmalRequlslte Faciritles - t,tirization of spent Aruminium Chloride generated during manufacturing ofCpC 6reen and 2,4 5-Trimethyl Benzoyl Chtoride
1.+ Copper as Cu mg/kC 923 15 Chromium as Cr mgKg 0.56 16 Manganese as Mn mgkg 2.14 Organi Compound '11 CPC- Blue mg&g 6.6 18 CPC- Green mgikc 9.8 19 Ferric Chloride mdkg 0.08
Characteristics ofSpent Aluminium Chloride Solution Generated from 2, 4, 6_Trimethyl Benzoyl Chloride Manufacturing Industries
S. No. Parameters Unit Result
Moisture Va 72.30 Aluminium Chloride 2 as AlCl3 Va 25.20 3 HCl',e 1.294 V-salt (as Sodium 4 Chloride) 7a 1.1
5 Calcium Chloride Va < 0.1 6 TOC mg/kg 66.50 Ileavv Mr)tals 7=--l Mercurv as Hs l mg&g < 0.1 -8-l Arsenic as As I mg/kg < 0.1 9 Cadmium as Cd mpyl(g 0.13 10 l-ead as Pb mdks 0.44 11 | Iron as Fe 5.16 1.2 Zinc as Zn 0.78
13 1 ftppr, Cu r.92 I ". 14 Chromium as Cr 0.46 15 | Manganese as Mn 0.94 ganic (lompound Acetyl Choride 16 1 mgkg < 0.1 Mesitylene s{, 2,4,6-'triMethyl 18 Benzoyl Chloride mgkg 10.90'
43.zUUIzs!e! hs!e$ The utilisation process shall involve following steps:
Woste Monagement-t! Division, C7CB Dethi 4lPage standard operating Proc€dure and checktist ofMinimarR€qursite Faciriries - u*ization otSpent aruminrum chloride generated during manufacruring ofCpCGr€en ana Z, + O_frimethyfaenro"ian,ond. ,", of Spenr Atuminium "j_y111,:lrion_ Chloride generated ftom 2, 4, 6_Trimethyl Denzoyr3:::, Lnronde, the spent solution is tmnsfered into thg pre-treatme't unit where the Spent Aluminium Chloride is treated with a.ri".t.a ,5'*rn"". Joiou, uno orguni. impudties- The treated Spent Aluminium Chloride is""ru"" then charged inait"-r.u"uon u"r."t and the other mw materials i.e alumina/aluminium hydroxide, iodium hfdroxioe Tsodium bi-carbonate / sodium carbonate and calcium f,ya.o"ia" luri in ioifi ur" uaa"O into reaction vessel in stage wise "oriJ manner._The solution is il,pt lrr the r"*ll":,pfoces\ is compteted in 04-05 houri. ffreicompterion"git"ri;i, "omptete or proce,... rne:::._,::1,1. reaclton mass is fillered rhrough [ilrer press. The producr i.e. Aluminium hldroride is obtained as liquid. The solid cake obtained frorn filter press is senj to if,. iSOn fo, finof disposal. The fumes from the reaction vessel are treated through venturi scrubber and the scrubbed bleed generated from venturi scrubber is further utili;ed in process io, ,nainiainins DU.
Alurninum Chloride
Spent Aluminium Chloride Pre-treatment unit (using activated carbon)
Alumina/Aluminium Filter Press (optionat if, acuvated carbon is in powderform) Hydroxide Sludge to TSDF
Sodium Hydroxide/Sodium Bi Scrubber Carbonate/Sodium Carbonate
Calcium Hydroxide Filter Press
Product i.e. Aluminium Hydroxide Chloride /Poly Aluminium Chloride
(b) In. case of utilisation of Spent Alumjnium Chloride generated from CpC grcen, the spent solution is firstly charged into the reaction vessel anojl" ott ,u* .ut"r-ials i.e iron scrap and sodium hydroxide "r /sodium bi-carbonate / sodium carbonate are adJed into ,eaction vessel. The solution is kept in agitatioD to comprete the reaction and the reacted mass is f tered through filter prcss. The filtered precipitaie is dried and tut"n oui. rt" iirtrut" solution from
woste Manogemenut Division, CpCB Delhi 5lPage Standard operating Procedure and checklist of Minimal Requlsit€ Facilities- utilization ofspent arumrnlum Chlorlde Senerated during manufacturinS ofCpC Green and 2" 4, 6-Trim€thyt Aenzoyt Chtoride
the filter press is further treated with activated carbon and transferred to the reaction vessel- and the other raw matetials i.e alumina/aluminium hydroxide, sodium hydroxide /sodium bi- carbonate / sodium carbonate and calcium hydroxide (all in solid form) are added into reaction vessel in stage wise matner. The solution is kept in agitation to complete the reaction. The reaction process is completed in 04-05 hours. After completion of prccess, the reaction mass is filtered through filter press. The product i.e, Aluminium hydroxide is obtained as liquid. The solid cake obtained from filter press is send to the TSDF for final disposal.
The fumes from the .eaction vessel (s) are treated through venturi scrubber and the scrubbed bleed generated from venturi scrubber is further utilized in prccess for maintaining pH.
Spent Al!minium Chloride
sodium Hydroxide/Sodium Bi Carbonate/Sodium Carbonate
StorageTank forAluminium Chloride
Pre-treatment unit (using activated carbon)
Filter Press (optional il actjvated carbon is in powderform)
Sodi!m hydroxide/Sodium Si Sludge to TSDF Carbonate/Sodium Carbonat€
Calcium Hydroxide
Product i.e. Aluminum Hydroxide Chloride/ Poly Aluminum Chtoride Slud8e to TSDF
Waste MonagenentJl Divjsion, CpCB Dethi 6lPage standard operatrng Procedure and checkrist of MinimarRequlsit€ Facilfles - utflrzation of spent aruminium Chlorlde tenerated during ma nufacturing ot CpC Green and 2,4 6_Trlmethyt Benzoyi Chtoride
43.3 Product Usase / Utilization
The liquid Aluminium Hydroxide Chloride/poly Aluminium Chloride will be utilized only in rhe Effluent.Treatment pulp Plant as coagulant and and paper industry as sizing material ani in no case shall be used iD Water Treatment plant.
product The i.e. Aluminium Hydroxide Cl oride poly Aluminium Chloride shall comply with the Bureau of Indian Standards: IS 15573:2018 for TOC i.e g0 ppm ( in liquid fom).
The unit shall label its produc-t (i.e. Aluminium Hydroxide Chloride /poly Aluminum Chloride) ,,This manufactued by utilizing aforesaid hazardous waste) as Aluminum hydroxide/poly Aluminum Chloride has been manufactured by utilizing Spent Aluminium Chloride and not to be used in Water Treatrnent plant,,.
43,4 Standard Operatinq Procedure (Sop) for utilization
This SoP is applicable only for the utilization of Spent Aluminium Chloride generated during manufacturing of CPC Green and 2, 4, 6-Trimethyl Benzoyl Chloride to produce Aluminium Hydro\ide Chloride Poly AJuminir_rm Chtoride 1in liquid form only,).
(1) The spent Aluminum chloride shall be transported in acid proof tankers mounted on vehicles,fitted with rcquisite safeguards ensuring no .pillug", as authorized by sPcB/"cc. (2) There sholld be a designated space for unloading of Spent Aluminum Chloride into a acid proof storage tank. The receiving storage tanli shall be placed above the ground and contained..with low raise parapevbund wall & concrete/acid proof floor with slope to collect spillages, if any into collection pit. (3) The.storage tank shall be kept under cool, dry, well- ventilated covered storage shed(s) within the ptemises, as authorised by the concerned State pollutio; Contrj Board/Pollution Control Committee under the Hazardous and Other Wastes (Management & Transboundary Movement) Rules, 2016, so as to eliminate min water rnIrus10n.
(4) There shall be no manual hatdling of the Spenr Aluminium Chloride and poty l]:riitul Chloride. Acid proof pump shall be used for rransfer.of Spent Aluminium Chloride through pipelines. (5) The Spent Aluminum Chlo de shall be transfer through mechanized system into the pre_ trcaknent unit to remove color and organic impudties by treating the Spent Aluminum Chloride with Activated Carbon.
In case of the Spent Aluminum Chloride generated from CpC green manufacturing proc€ss, tne prc-trcatmett with Activated Carbon shall be carried after removal of Coppei from the Spent Aluminum Chloride by treating the same with ircn scrap and sod'ium
Waste MondgementJl Division, C\CB Delhj TlPage dgL ., Standard Op€ratlng Procedure and Ch€cktist of MtntmalRequisit€ Fac ities - Utitilation ofSDent Atumlntum Ch loride generated during manufactu ring of CpC Gre€n and 2, 4, 6-Trimethyt Benzoyl Ch loride
hydroxide in the mechanized agitated rgaction vessel. The same should added through closed conveyor system The reacted mass shall be transferred to the filter press and precipitated solid mass from the filter press is dried and packed and kept in Stonge area. (6) The activated carbon treated Aluminum Chlo de solution shall be transferrcd to the closed reaction vessel where alumina/aluminium hydroxide, sodium hydroxide /sodium bi-carbonate / sodium carbonate and calcium hydroxide are also added step by step in powder form into the reactor through closed conveyor system. The reactor shall be of acid prcof material.
(1) The solution in the reactor shall be agitated with the help of mechanized agitator for 4-4.5 houls and then tmnsferred to filter press through pump for filtration. The solid mass from the filter press shall be removed mechanically and packed and kept in storage area.
(8) The Filtrate i.e Liquid Aluminium hydroxide is received as the final product from the filrer press.
(9) Acid fume/vapor is expectgd to be liberated from the reaction tanks whgre ircn alumina/aluminium hydroxide, sodium hydroxide /sodium bi_carbonate / sodium carbonate and calcium hydroxide is added to Spent Aluminium Chloride solution. Thus, the said reaction tanks shall be connected with hood over it to suck acid fume/vaoour. The hood shall be maintained under suction followed by trcatment in scrubber using alkaline medium and attached to stack of minimum height of 06 m above the roof top oi as prescdbed by the concerned SpCB/pCC, whichever is higher. (10) The entire prccess area shall have leak-proof and acid proof floor tiles with adequate slope. to collect spillages, if any, a collection pit. _into The spillages from collection pit shall be transferrcd to reaction tank, as the cases may be, through aiid proofpump. (11) The prodxct i.e. Alumjnium Hydroxide Cl oride /poly Aluminium Chloride shall comply with the Bureau of Indian Srandards: IS 15573:2018 for TOC i.e 80 ppm (liquid form). (12) The product (i.e. Aluminium Hydroxide Chloride /poly Aluminum Chloride) manufactured by utilizing aforesaid hazardous waste shall only be used pulp in ETp as coagulant and & paper industry as sizing agent. (13) The unit shall label irs product (ie. Aluminium Hydroxide Chlo de /poly Aluminum Chloride) manufactured by utilizing aforesaid hazardous waste) as ..t.his Aluminum hydroxide/Poly Aluminum Chloride. has been rnanufacturej by utilizing Spent Aluminium Chloride and not to be used in Water Treatment plant,, (14) The unit. shall maintain proper ventilation in the work zone and process areas. All in.lhe ptanr operarion sha wear proper personal prorecti\ e equipmenl trrE)ffl.jlTly::l::d (15) Treatment and disposal ofwastewaler: The pollution potentials are emissions from reactors and residues from tilter press and there is no generation of wastewater and ther"ofon ai"at urg" oiru.t"Jut"r. Woste Manogementll Division, CpCB Dethi 8lPage Mv Standard Operatlng P.ocedure and Checktist of Minimal Requisite Facitities_ U lization ofSpent atumhtum Chlorlde generated during ma nufacturtnt of CpC Green and 2,4,6_Trimethyt BenroylChtoride (16) It shall be ensured that Spent Aluminium Chloride is procured from rhe indusrries that have valid authorization for the same from the concemed SPCB/PCC as required under Hazardous and Other Wastes (Management and Transboundary Movement) Rules, 2016. (17) Transpoftation of Spent Aluminum Chloride and residues generated during utilisation shall be caried out by the sender or rcceiver (utilizer/TsDF operator) as per the authorization issued by concemed SPCB//PCC under the Hazardous and Other Wastes (Management & Transboundary Movement) Rules, 2016 and in compliance with other provisions of said rules. (18) The residue generated from filter press during Copper removal shall be sent to SPCB,/PCC authorised rccycler/utiliser or disposed in SpCB/pCC authorized common or captive disposal facility. (19) Th€ other residue genemted from (filter press), product spillages etc. shall be collected and temporarily stored at designated place with proper cover and concrete/acid proof brick lining floor and be sent to authorized common TSDF or other authoized facility within 90 days from geneEtion of the waste in accordance with the authorization issued by the concemed SPCB/PCC. Such storage area shall be covered with proper ventilalion. (2O) [n case of environmental damages arising due to improper haDdling of hazardous wastes including accidental spillage during generation, stoiuLge, processing, tmnsportation and disposal, the unit shall be liable to implement immediatc response measuresr envlronmental site assessment and remediation of contaminated ,,Guidelines soil/groundwater/sediment etc. as per the on Implementing Liabiliries fbr Environrnental Damages due to Haldling & Disposal of Hazar-dous Wasles ard penalty,. published by CPCB. (21) During the process of utilization and handling of hazardous waste, the unit shall comply with the requirements in accordance with the public Liability Insurance Act, 1991 as amended, wherever applicable. 43,5 Records/Return lilins (1) The unit shall maintain a passbook issued by concerned SPCB wherein the following details of each procurement of Spent Aluminium Chloride shall be entered: - Address of the sender . Dare of dispalch - Ouantity procured - Seal and signature of the sender - Date of receipt in the premises (2) A log book with info.mation on source and date of procurement of each type of the said hazardous wastes, quantity, date wise utilization of the same, quantity of Aluminium Hydroxide Chlo de/Poly Aluminium Chlo de manufactured, hazardous . waste Woste MonagementJt Division, C?CB Delhi #-j2-' n Standard Operallng Procedure and Checklist of Minimal Requisite facilities- Utilization ofSpent Aluminlum Chloride generated durlng manufacturing ofCPC Gr€en end 2, 4, 6-Trimethyl aenzoyl Chloride generation and its disposal etc. shall be maintained including analysis report of emission- monitoring & effluent discharged, as applicable. (3) The unit shall maintain record of hazardous waste utilised, hazardous waste generated and disposed as per Form 3 & shall file annual retums in Form 4 as per Rule 20 (1) and (2) of the Hazardous and Other Wastes (Management and Transboundary Movement) Rules. 2016. to concerned SPCB. (4) The unit shall submit quarterly and annual infomation on hazardous wastes consumed, its source, products generated or resources conserved (specifying the details like, tlpe and quantity of resources conserved) to the concerned SPCB. 43.6 Standards (1) Fugitive emissions in the work zone shall comply with the following: PMlO - 5 mg/m3 TWA* HCt - 7 mg/m3 Ceiling# TWA* - Time-weighted average The Pemissible Exposufe Limit is 8-hour TWA. # A Ceiling limit is one that may not be exceeded for any period of time, and is applied to irritants and other materials that have immediate effects (Reference: Occupational Safety and Health Standaftts 1910:1000); (2) Source Emission in Stack attached to the feaction tanks shall comply with the following: PM - 50 mg/Nm3 HCI Vapour & Mist - 35 mg/Nm3 TOC - 20 mg/Nm3 (3) Monitoring of specified paramete.s for source and fugitive emission shall be carried out by NABL accredited or ISO17025/EPA recognized laboratories and the results shall be submitted quarterly to the concerned SPCB/PCC. 43.7 Sittine of Industry Facilities processing for of Spent Aluminium Chloride shall prefenblv be located in a notified industrial area or indusrrial park.estate/cluster. */2 Wdste Monagement-lt Division, C7CB Delhi l0 lPas e ' Standard Operating Procedure and Checklist ol Mlnimal Requlsite Facilities- Utilization of Spent Atuminium Chloride g€nerated during manufacturtng ofCpgcreen and 2,4 S-frimethyl BenzoytChtorlde 43.8 Size of Plant & Efficiencv of utilisation About 23030 Kgs of Spent Aluminium Chlodde (generated ftom 2, 4,6-Trimethyl Benzoyl Chloride) alongwith other mate al would be required to produce 25140 Kgs of Aluminum Hydroxide Chloride and 18260 Kgs of Spent Aluminium Chlo.ide (generated ftom CpC Green) alongwith other matedal would required to produce 18800 Kgs of Aluminum Hydroxide Chloride. Therefore, requisite facilities of adequate size shall be installed accordingly as mentioned under para 43.10 below. 43.9 OnJine detectors i Alarms / Analvzers In case of continuous process opemtions, online analysers shall be installed for pM aDd TOC in the stack emission. The onJine data shall be connected to the concemed SPCB/PCC server. 43.10- Checklist of Minimal Reouisite Facilities S. No. Requisite Facilities 1. Storage shed(s) for storage of Spent Aluminium Chloride in acid proof container only under cool, dry, well-ventilated covered stomge shed(s) within premises. 2. Separate Storage area for stonge of liquid Aluminium Hydroxide Chloride /poly Aluminium Chloride 3. Storage Tanks should be of such size/capacity that it can store two weeks requirements 4. Collection pit for collection of the spillage from storage area, process area and unloadine area. 5. Closed Mechanized system for - - mixing of Spent Aluminium Chloride with alumina/aluminium hydroxide, sodium hydroxide /sodium bi-carbonate / sodium carbonate and calcium hydroxide. - transfer of alumina,/aluminium hydfoxide, sodium hydroxide /sodium bi-carbonate / sodium carbonate and calcium hydroxide into process rcactor _ 6. Chemical process pumps (acid proo0 for tmnsfer of Spent Aluminium Chloride and Poly Aluminium Chloride from tanker to storage tank and subsequently to process area 7. Activated Carbon Pre-trcatment unit Filter press (optional in case activated carbon used in powder form) 8. Closed Process reactor (reaction vessel (s)) attached to scrubbing system followed by stack of minimum height of 06 m above the roof top or as prescribed bv Woste Mondgement- Division, CqCB Delhi 11 lPage i Standard Op€reting Procedure and Checklist of Mlnlmal Req ulslte Facilities- Utilization ofSpent Alumlnlum Chloride generated during manufacturlng of CPC Green and 2,4 5-Trimethyl BenzoylChloride concefned s whichever is 9. Filter Press 10. Dedicated separate covered hazardous waste (filter press residue, activated carbon, etc.) storage area to store hazardous generated during utilization process 11. Stacks to have sampling port, platform, access to the platform etc. as per the Guidelines on Methodologies lor Source Emission Monitoring published by CPCB under Inboratory Analysis Techniques I,ATS/80/2013-14. 12. Product shall be stored in cool, dry, well-ventilated covered storage shed within premlses. 13. Online analysers shall be installed for PM and TOC in the stack emission and be connected to the concerned SPCB/PCC scrver. Woste Monogementll Division, CqCB Dethi 12 lPage ApoendixA Manufacturinq orocess of 2,4.6Tri Methvl BenzolcAcld Mesitylene-120.2 Kg Aluminum Chloride-133.34 Kg Water-108 Kg 2,4,6 TriMethyl Aluminum Chloride Behzoic Acid- Solution-241.34 Kg 764.2 Kg tat a.a 'l; :]tVri: 1:, E d s \ ; I d F .t' . o E )t a . . :: 5 ....:,.